2986
T. Yıldız, A. Yusufog˘lu / Tetrahedron: Asymmetry 21 (2010) 2981–2987
for (R), 93.3% for (S). IR (neat, cmꢂ1): 3372, 3030, 2946, 2865, 1675,
1483, 1402, 1316, 1050, 779, 698 cmꢂ1 1H NMR (CDCl3): d 0.82 (t,
4.5.9. (S)-1-(p-Methoxyphenyl)-1-tetradecanol 2j
.
Mp 44.9–45.4 °C, ½a D25
¼ ꢂ17:2 (c 1.1, chloroform). HPLC anal-
ꢁ
3H, J = 6.8 Hz), 1.12–1.29 (m, 24H), 1.62–1.70 (m, 2H), 1.85 (br s,
1H), 4.56 (t, 1H, J = 7.8 Hz), 7.16–7.27 (m, 5H). 13C NMR (CDCl3):
d 14.31, 22.90, 26.05, 29.56–29.90, 32.14, 39.35, 74.94, 126.11,
127.69, 128.64, 145.19. MS m/z: 43, 69, 79, 91, 107, 120, 133,
286, 304, 305 (M+). Anal. calcd for C21H36O: C, 82.83; H, 11.92.
Found: C, 82.99; H, 12.94.
ysis: Chiralcel OD chiral column, mobile phase iso-PrOH/hexane:
2:98, flow rate: 1.0 ml/min, wavelength: 210 nm; Rt (retention
time): 12.174 min for (R)-isomer, 12.926 min for (S)-isomer; pur-
ity: 1.8% for (R), 98.2% for (S). IR (neat, cmꢂ1): 3307, 3069, 2923,
2853, 1623, 1461, 1307, 1253, 1107, 1046, 807, 723 cmꢂ1 1H
.
NMR (CDCl3): d 0.82 (t, 3H, J = 6.3 Hz), 1.12–1.35 (m, 22H), 1.50
(br s, 1H), 1.58–1.75 (m, 2H), 3.72 (s, 3H), 4.55 (t, 1H,
J = 6.8 Hz), 6.80 (dd, 2H, J1 = 1.9, J2 = 6.8 Hz), 7.16 (dd, 2H,
J1 = 1.9, J2 = 6.8 Hz). 13C NMR (CDCl3): d 14.40, 23.01, 26.20,
29.40–30.01, 32.20, 39.05, 55.03, 75.00, 114.01, 115.09, 125.54,
139.19, 159.20. MS m/z: 43, 44, 69, 94, 121, 137, 147, 320 (M+),
321. Anal. calcd for C21H36O2: C, 78.70; H, 11.32. Found: C,
78.16; H, 10.97.
4.5.5. (S)-1-Phenyl-1-hexadecanol 2e
Mp 60.5–61.2 °C, ½a D25
¼ ꢂ19:6 (c 1.1, hexane). HPLC analysis:
ꢁ
Chiralcel OD chiral column, mobile phase iso-PrOH/hexane: 2:98,
flow rate: 1.0 ml/min, wavelength: 210 nm; Rt (retention time):
9.204 min for (R)-isomer, 11.078 min for (S)-isomer; purity: 4.5%
for (R), 95.5% for (S). IR (neat, cmꢂ1): 3372, 3043, 2946, 2854,
1669, 1483, 1402, 1316, 1023, 779, 698 cmꢂ1 1H NMR (CDCl3): d
.
0.85 (t, 3H, J = 6.8 Hz), 1.12–1.30 (m, 26H), 1.72–1.82 (m, 2H),
1.95 (br s, 1H), 4.68 (t, 1H, J = 7.3 Hz), 7.28–7.36 (m, 5H). 13C
NMR (CDCl3): d 14.31, 22.90, 26.05, 29.56–29.90, 32.14, 39.35,
74.94, 126.11, 127.69, 128.64, 145.19. MS m/z: 43, 55, 69, 79,
107, 120, 133, 207, 316, 318 (M+). Anal. calcd for C22H38O: C,
82.95; H, 12.03. Found: C, 82.84; H, 13.45.
4.5.10. (S)-1-(p-Bromophenyl)-1-tetradecanol 2k
Mp 42.7–43.1 °C, ½a D25
¼ ꢂ15 (c 1.1, chloroform). HPLC analysis:
ꢁ
Chiralcel OD chiral column, mobile phase iso-PrOH/hexane: 2:98,
flow rate: 1.0 ml/min, wavelength: 210 nm; Rt (retention time):
10.249 min for (S)-isomer, 10.589 min for (R)-isomer; purity:
99.6% for (S), 0.4% for (R). IR (neat, cmꢂ1): 3353, 3069, 2923,
2846, 1600, 1476, 1353, 1223, 1130, 1076, 823, 723 cmꢂ1 1H
.
NMR (CDCl3): d 0.80 (t, 3H, J = 6.8 Hz), 1.12–1.34 (m, 22H), 1.54–
1.72 (m, 2H), 1.80 (br s, 1H), 4.53 (t, 1H, J = 7.3 Hz), 7.14 (dd, 2H,
J1 = 1.9, J2 = 6.3 Hz), 7.39 (dd, 2H, J1 = 1.9, J2 = 6.3 Hz). 13C NMR
(CDCl3): d 14.50, 23.50, 26.20, 29.80–30.01, 32.20, 39.40, 74.00,
121.01, 127.90, 131.80, 144.19. MS m/z: 43, 55, 77, 106, 120, 157,
185, 368, 369 (M+). Anal. calcd for C20H33BrO: C, 65.03; H, 9.00.
Found: C, 65.41; H, 9.09.
4.5.6. (S)-1-Phenyl-1-nonadecanol 2f
Mp 50.5–51 °C, ½a D25
¼ ꢂ18:4 (c 1.1, hexane). HPLC analysis:
ꢁ
Chiralcel OD chiral column, mobile phase iso-PrOH/hexane: 2:98,
flow rate: 1.0 ml/min, wavelength: 210 nm; Rt (retention time):
9.555 min for (R)-isomer, 11.677 min for (S)-isomer; purity:
13.9% for (R), 86.1% for (S). IR (neat, cmꢂ1): 3407, 3025, 2947,
2861, 1686, 1483, 1409, 1325, 1077, 752, 698 cmꢂ1 1H NMR
.
(CDCl3): d 0.80 (t, 3H, J = 6.8 Hz), 1.12–1.25 (m, 32H), 1.56–1.68
(m, 2H), 1.82 (br s, 1H), 4.60 (t, 1H, J = 7.3 Hz), 7.17–7.27 (m, 5H).
13C NMR (CDCl3): d 14.31, 22.90, 26.05, 29.57–30.01, 32.14,
39.35, 74.95, 126.11, 127.69, 128.64, 145.19. MS m/z: 43, 69, 79,
91, 107, 120, 147, 207, 342, 358 (M+). Anal. calcd for C25H44O: C,
82.26; H, 12.30. Found: C, 81.39; H, 12.82.
4.5.11. (S)-1-(p-Hydroxyphenyl)-1-tetradecanol 2m
Mp 66.2–67.1 °C, ½a D25
¼ ꢂ15:2 (c 1.1, chloroform). HPLC analy-
ꢁ
sis: Chiralcel OD chiral column, mobile phase iso-PrOH/hexane:
5:95, flow rate: 1.0 ml/min, wavelength: 210 nm; Rt (retention
time): 20.772 min for (R)-isomer, 23.017 min for (S)-isomer; pur-
ity: 7% for (R), 93% for (S). IR (neat, cmꢂ1): 3407, 3030, 2923,
2853, 1630, 1469, 1307, 1284, 1123, 1053, 807, 723 cmꢂ1 1H
.
4.5.7. (S)-1-Phenyl-1-Eicosanol 2g
Mp 70.2–71 °C, ½a D25
¼ ꢂ17 (c 1.1, hexane). HPLC analysis: Chi-
ꢁ
NMR (CDCl3): d 0.82 (t, 3H, J = 6.8 Hz), 1.12–1.34 (m, 22H), 1.49
(br s, 1H), 1.56–1.76 (m, 2H), 4.45 (t, 1H, J = 6.8 Hz), 4.70 (br s,
1H), 6.74 (dd, 2H, J1 = 1.9, J2 = 6.3 Hz), 7.18 (dd, 2H, J1 = 1.9,
J2 = 6.3 Hz). 13C NMR (CDCl3): d 15.00, 23.10, 26.00, 29.40–30.01,
31.20, 38.30, 73.50, 114.20, 126.20, 136.10, 154.19. MS m/z: 41,
65, 77, 95, 107, 123, 133, 305, 306 (M+). Anal. calcd for C20H34O2:
C, 78.38; H, 11.18. Found: C, 78.22; H, 11.57.
ralcel OD chiral column, mobile phase iso-PrOH/hexane: 2:98, flow
rate: 1.0 ml/min, wavelength: 210 nm; Rt (retention time):
8.254 min for (R)-isomer, 10.038 min for (S)-isomer; purity: 4.8%
for (R), 95.2% for (S). IR (neat, cmꢂ1): 3407, 3040, 2946, 2871,
1685, 1483, 1409, 1325, 1050, 752, 698 cmꢂ1 1H NMR (CDCl3): d
.
0.85 (t, 3H, J = 6.8 Hz), 1.15–1.30 (m, 34H), 1.44 (br s, 1H), 1.61–
1.72 (m, 2H), 4.70 (t, 1H, J = 7.3 Hz), 7.27–7.37 (m, 5H). 13C NMR
(CDCl3): d 14.31, 22.90, 26.05, 29.57–30.01, 32.14, 39.35, 74.94,
126.11, 127.69, 128.64, 145.19. MS m/z: 43, 57, 79, 91, 107, 120,
147, 207, 356, 374 (M+). Anal. calcd for C26H46O: C, 83.35; H,
12.66. Found: C, 83.19; H, 13.36.
4.5.12. (S)-1-(2-Furyl)-1-hexadecanol 2n
Mp 58.5–59.4 °C, ½a D25
¼ ꢂ11 (c 1.1, chloroform). HPLC analysis:
ꢁ
Chiralcel OD chiral column, mobile phase iso-PrOH/hexane:
1.5:98.5, flow rate: 1.0 ml/min, wavelength: 210 nm; Rt (retention
time): 10.221 min for (R)-isomer, 11.137 min for (S)-isomer; pur-
ity: 2.2% for (R), 97.8% for (S). IR (neat, cmꢂ1): 3346, 3023, 2923,
4.5.8. (S)-1-(p-Methylphenyl)-1-tridecanol 2h
2853, 1607, 1476, 1276, 1153, 1107, 1046, 846, 753 cmꢂ1 1H
.
Mp 39.1–39.7 °C, ½a D25
¼ ꢂ28:6 (c 1.1, chloroform). HPLC analy-
ꢁ
NMR (CDCl3): d 0.82 (t, 3H, J = 6.8 Hz), 1.14–1.42 (m, 27H), 1.74–
1.82 (m, 2H), 4.70 (t, 1H, J = 6.8 Hz), 6.15 (dd, 1H, J1 = 1.0,
J2 = 3.4 Hz), 6.26 (dd, 1H, J1 = 1.9, J2 = 3.4 Hz), 7.30 (dd, 1H,
J1 = 1.0, J2 = 1.9 Hz). 13C NMR (CDCl3): d 14.25, 23.10, 25.90,
29.80–30.01, 32.10, 36.10, 68.00, 106.20, 111.01, 142.10, 157.20.
MS m/z: 41, 69, 81, 97, 107, 121, 135, 290, 308 (M+), 309. Anal.
calcd for C20H36O2: C, 77.86; H, 11.76. Found: C, 77.01; H, 11.86.
sis: Chiralcel OD chiral column, mobile phase iso-PrOH/hexane:
1:99, flow rate: 1.0 ml/min, wavelength: 210 nm; Rt (retention
time): 16.679 min for (R)-isomer, 17.340 min for (S)-isomer; pur-
ity: 0% for (R), 100% for (S). IR (neat, cmꢂ1): 3392, 3038, 2923,
2853, 1646, 1469, 1269, 1261, 1107, 1046, 823, 738 cmꢂ1 1H
.
NMR (CDCl3): d 0.80 (t, 3H, J = 6.8 Hz), 1.14–1.40 (m, 20H), 1.50
(br s, 1H), 1.58–1.80 (m, 2H), 2.28 (s, 3H), 4.68 (t, 1H, J = 7.3 Hz),
7.09 (d, 2H, J = 7.8 Hz), 7.16 (d, 2H, J = 7.8 Hz). 13C NMR (CDCl3):
d 14.20, 21.30, 23.01, 26.20, 29.00–30.01, 32.20, 39.35, 74.80,
126.01, 129.69, 136.54, 142.19. MS m/z: 41, 57, 77, 93, 121, 131,
145, 272, 288, 290 (M+). Anal. calcd for C20H34O: C, 82.69; H,
11.80. Found: C, 82.41; H, 11.63.
4.5.13. (S)-1-(2-Thenyl)-1-hexadecanol 2p
Mp 44.9–45.4 °C, ½a D25
¼ ꢂ15:2 (c 1.1, chloroform). HPLC analy-
ꢁ
sis: Chiralcel OD chiral column, mobile phase iso-PrOH/hexane:
1.5:98.5, flow rate: 1.0 ml/min, wavelength: 210 nm; Rt (retention